WO2018088079A1 - 化合物、薄膜形成用原料、薄膜の製造方法及びアミジン化合物 - Google Patents

化合物、薄膜形成用原料、薄膜の製造方法及びアミジン化合物 Download PDF

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WO2018088079A1
WO2018088079A1 PCT/JP2017/036318 JP2017036318W WO2018088079A1 WO 2018088079 A1 WO2018088079 A1 WO 2018088079A1 JP 2017036318 W JP2017036318 W JP 2017036318W WO 2018088079 A1 WO2018088079 A1 WO 2018088079A1
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thin film
compound
group
carbon atoms
alkyl group
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PCT/JP2017/036318
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English (en)
French (fr)
Japanese (ja)
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智晴 吉野
奈奈 杉浦
章浩 西田
敦史 山下
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株式会社Adeka
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Priority to IL266365A priority Critical patent/IL266365B2/en
Priority to EP17868933.7A priority patent/EP3539973A4/en
Priority to CN201780068589.0A priority patent/CN109923119B/zh
Priority to JP2018550070A priority patent/JP7075891B2/ja
Priority to US16/346,724 priority patent/US11161867B2/en
Priority to KR1020197015045A priority patent/KR102503603B1/ko
Publication of WO2018088079A1 publication Critical patent/WO2018088079A1/ja
Priority to US17/490,227 priority patent/US11618762B2/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/06—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
    • C07C251/08—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton being acyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/14—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD

Definitions

  • the present invention relates to a novel compound, a thin film forming material containing the compound, a method for producing a thin film using the thin film forming material, and a novel amidine compound.
  • Thin film materials containing metallic elements are applied to various applications because they exhibit electrical properties, optical properties, and the like.
  • copper and copper-containing thin films are applied as wiring materials for LSIs because of their properties of high conductivity, high electromigration resistance, and high melting point.
  • Nickel and nickel-containing thin films are mainly used as members of electronic parts such as resistive films and barrier films, members for recording media such as magnetic films, and members for thin film solar cells such as electrodes.
  • Cobalt and cobalt-containing thin films are used for electrode films, resistance films, adhesive films, magnetic tapes, cemented carbide tools and the like.
  • Examples of the method for producing the above-mentioned thin film include a sputtering method, an ion plating method, a coating thermal decomposition method, a MOD method such as a sol-gel method, and a chemical vapor deposition method.
  • a sputtering method an ion plating method
  • a coating thermal decomposition method a coating thermal decomposition method
  • a MOD method such as a sol-gel method
  • a chemical vapor deposition method since it has many advantages such as excellent composition controllability, step coverage, suitable for mass production, and hybrid integration, atomic layer deposition (hereinafter referred to simply as ALD (Atomic Layer) Chemical vapor deposition (hereinafter, also simply referred to as CVD) including the method sometimes referred to as “deposition” is an optimal manufacturing process.
  • ALD Atomic Layer
  • CVD Chemical vapor deposition
  • Patent Document 1 discloses a method of forming a thin film containing metal using volatile metal amidinate.
  • Patent Document 2 discloses a diazadiene-based metal compound that can be used for a chemical vapor deposition method or an atomic layer deposition method. Patent Document 1 and Patent Document 2 do not describe the compound of the present invention at all.
  • the material for forming a thin film which has a high vapor pressure, a low melting point and can produce a high quality metal-containing thin film Is required. None of the conventionally known raw materials for thin film formation show such physical properties. Among them, in order to improve the productivity, it is necessary to improve the transportability of the thin film forming material, and therefore, a material having a low melting point has been strongly demanded.
  • the present invention provides a compound represented by the following general formula (1), a raw material for forming a thin film containing the compound, and a method for producing a thin film using the raw material.
  • R 1 represents a linear or branched alkyl group having 1 to 5 carbon atoms
  • R 2 represents hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms
  • R 3 And R 4 each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms
  • A represents an alkanediyl group having 1 to 4 carbon atoms
  • M represents copper, iron, nickel, cobalt or Represents manganese.
  • the present invention also provides an amidine compound represented by the following general formula (2).
  • R 5 represents a linear or branched alkyl group having 1 to 5 carbon atoms
  • R 6 represents hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms
  • R 7 And R 8 each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms
  • L represents an alkanediyl group having 1 to 4 carbon atoms, provided that R 5 is an ethyl group and
  • R 6 is hydrogen, L is a branched alkanediyl group having 3 carbon atoms, or an alkanediyl group having 4 carbon atoms, and R 5 is an ethyl group or a tertiary butyl group and R 6
  • L is a methyl group
  • L is an alkanediyl group having 3 or 4 carbon atoms.
  • the present invention it is possible to obtain a compound having a high vapor pressure, and a low melting point which becomes liquid at normal pressure of 30 ° C. or slight heating.
  • the compound is particularly suitable as a raw material for forming a metal-containing thin film by the CVD method, and can be preferably used as a raw material for forming a metal-containing thin film by the ALD method.
  • the cobalt-containing compound of the present invention is used as a raw material for thin film formation by the ALD method, since the cobalt-containing thin film is not formed on the surfaces of the silicon substrate and the silicon oxide substrate, the silicon substrate and the oxide are oxidized.
  • a cobalt-containing thin film can be selectively formed only on a pattern of a copper layer or a ruthenium layer. Further, according to the present invention, an amidine compound which can be used to synthesize the above-mentioned compound can be obtained.
  • FIG. 1 is a schematic view showing an example of an apparatus for chemical vapor deposition used in the method for producing a thin film according to the present invention.
  • FIG. 2 is a schematic view showing another example of the apparatus for chemical vapor deposition used in the method for producing a thin film according to the present invention.
  • FIG. 3 is a schematic view showing another example of the apparatus for chemical vapor deposition used in the method for producing a thin film according to the present invention.
  • FIG. 4 is a schematic view showing another example of the apparatus for chemical vapor deposition used in the method for producing a thin film according to the present invention.
  • the compound of the present invention is a compound represented by the above general formula (1), which is suitable as a precursor of a thin film production method having a vaporization process such as a CVD method, and a thin film is formed by using the ALD method. You can also.
  • the compounds of the present invention are low melting point compounds which are liquid at normal pressure of 30 ° C. or liquid at slight heating.
  • a compound having a low melting point is suitable as a precursor of a thin film production method having a vaporization step such as a CVD method because the compound has good transportability.
  • Examples of the linear or branched alkyl group having 1 to 5 carbon atoms represented by R 1 , R 2 , R 3 and R 4 in the above general formula (1) include, for example, methyl group, ethyl group, propyl Groups, isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, pentyl group, isopentyl group and the like.
  • Examples of the alkanediyl group having 1 to 4 carbon atoms represented by A in the general formula (1) include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group. Groups, butylene group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2-diyl group and the like.
  • M represents copper, iron, nickel, cobalt or manganese.
  • a compound in which M is copper, cobalt or nickel is preferable because it can form a thin film having a low melting point and a low residual carbon content by the ALD method, and in particular a compound in which M is cobalt, high quality cobalt atom containing It is preferable from the ability to form a thin film.
  • R 1 is a secondary or tertiary alkyl group having 3 to 5 carbon atoms are preferable because of their low melting points, and R 1 is preferably a tertiary alkyl having 3 to 5 carbon atoms.
  • Compounds which are groups are particularly preferred.
  • Compounds of the above general formula (1) in which R 2 is hydrogen, a methyl group or an ethyl group are preferable because they have a low melting point and a high vapor pressure. Among them, compounds in which R 2 is a methyl group are particularly preferable.
  • a compound in which R 3 and R 4 are a methyl group or an ethyl group is preferable because of its low melting point and high vapor pressure.
  • compounds in which R 3 and R 4 are methyl groups are particularly preferable.
  • Compounds of the above general formula (1) in which A is an ethylene group, a propane-1,3-diyl group or a propane-1,2-diyl group are preferable because they have a low melting point and a high vapor pressure.
  • compounds in which A is a propane-1,2-diyl group are particularly preferable.
  • R 1 to R 4 and A can be appropriately selected depending on the solubility in the solvent used, the thin film formation reaction and the like.
  • Preferred specific examples of the compound in which M is cobalt in the above general formula (1) include, for example, the compounds No. 1 and 2 below. 1 to No. 18 can be mentioned.
  • compound No. 1 As preferable specific examples of the compound in which M is copper in the above general formula (1), for example, compound No. 1 below can be used. 19 to No. 36 can be mentioned. In addition, the following compound No. 19 to No. In 36, “Me” represents a methyl group, “Et” represents an ethyl group, and “tBu” represents a tertiary butyl group.
  • compound No. 1 As a preferable specific example of a compound in which M is nickel in the above general formula (1), for example, compound No. 1 below can be used. 37 to No. 54 can be mentioned. In addition, the following compound No. 37 to No. In 54, “Me” represents a methyl group, “Et” represents an ethyl group, and “tBu” represents a tertiary butyl group.
  • the compound of the present invention is not particularly limited by the method for producing it, and is produced by applying well-known reactions.
  • the amidine compound of the structure corresponding to cobalt (II) chloride is made to react in normal butyl lithium presence.
  • the raw material for thin film formation of the present invention is a precursor of the thin film formed by using the compound of the present invention described above as a precursor of the thin film, and the form differs depending on the manufacturing process to which the raw material for thin film formation is applied.
  • the raw material for thin film formation of the present invention does not contain metal compounds other than the above compounds. It is.
  • the raw material for forming a thin film of the present invention is a compound containing a desired metal and / or a metalloid (in addition to the above compounds Hereinafter, it is also referred to as other precursors).
  • the thin film forming material of the present invention may further contain an organic solvent and / or a nucleophile, as described later.
  • the physical properties of the compound which is a precursor are suitable for the CVD method and the ALD method, and particularly the raw material for chemical vapor deposition (hereinafter sometimes referred to as a raw material for CVD) Useful as.
  • the raw material for thin film formation of this invention is a raw material for chemical vapor deposition
  • the form is suitably selected by methods, such as a transport supply method of the CVD method to be used.
  • the CVD raw material is vaporized into a vapor by heating and / or depressurizing in a container (hereinafter, also simply referred to as a raw material container) in which the raw material is stored.
  • a container hereinafter, also simply referred to as a raw material container
  • Gas transport method for introducing the vapor into a film forming chamber (hereinafter also referred to as a deposition reaction unit) in which a substrate is installed, together with a carrier gas such as argon, nitrogen, or helium used accordingly
  • a carrier gas such as argon, nitrogen, or helium used accordingly
  • the raw material is transported in the form of liquid or solution to a vaporization chamber, vaporized by heating and / or depressurization in the vaporization chamber to turn into a vapor, and the vapor is introduced into the deposition chamber.
  • the compound represented by the above general formula (1) can be used as a raw material for CVD.
  • the compound represented by the above general formula (1) or a solution in which the compound is dissolved in an organic solvent can be used as a raw material for CVD.
  • These CVD materials may further contain other precursors, nucleophilic reagents and the like.
  • the method of vaporizing and supplying the raw materials for CVD independently for each component (hereinafter sometimes referred to as single source method) and the multi-component raw material were mixed in advance with a desired composition.
  • a method of vaporizing and supplying the mixed material (hereinafter sometimes referred to as a cocktail source method).
  • a cocktail source method a mixture of the compound of the present invention and another precursor or a mixed solution of the mixture in an organic solvent can be used as a raw material for CVD.
  • the mixture or mixed solution may further contain a nucleophile or the like.
  • organic solvents are not particularly limited, and known organic solvents can be used.
  • the organic solvent include acetic acid esters such as ethyl acetate, butyl acetate and methoxyethyl acetate; tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether, ethers such as dioxane; methyl Ketones such as butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone and methyl cyclohexanone; hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, dimethylcyclohexane, ethylcyclohexan
  • organic solvents may be used alone or in combination of two or more, depending on the solubility of the solute, the relationship between the operating temperature and the boiling point, the flash point, and the like.
  • the total amount of the precursor in the raw material for CVD which is a solution in which the precursor is dissolved in the organic solvent, is 0.01 to 2.0 mol / l, particularly 0.05 to 1.0 mol / l. It is preferable to use a liter.
  • the amount of the entire precursor is the amount of the compound of the present invention when the raw material for forming a thin film of the present invention does not contain a metal compound and a semimetal compound other than the compound of the present invention.
  • the raw material contains a compound containing another metal in addition to the compound and / or a compound containing a metalloid (other precursor), it is the total amount of the compound of the present invention and the other precursor.
  • the other precursors mentioned above are known in the art and their methods of preparation are also known.
  • the inorganic salt of the metal described above or the hydrate thereof is reacted with an alkali metal alkoxide of the alcohol compound, for example.
  • a precursor can be produced.
  • metal inorganic salts or hydrates thereof include metal halides, nitrates and the like
  • alkali metal alkoxides include sodium alkoxide, lithium alkoxide, potassium alkoxide and the like.
  • the other precursor mentioned above is preferably a compound having a similar thermal and / or oxidative degradation behavior to the compound of the present invention in the case of the single source method, and in the case of the cocktail source method, the thermal and / or oxidative degradation In addition to their similar behavior, those which do not cause deterioration due to chemical reaction or the like during mixing are preferred.
  • examples of the precursor containing titanium, zirconium or hafnium include compounds represented by the following formulas (II-1) to (II-5).
  • R c represents an alkyl group having 1 to 8 carbon atoms
  • R d represents an alkylene group having 2 to 18 carbon atoms which may be branched
  • R e and R f each independently represent
  • R g , R h , R k and R j each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • p is 0
  • q represents 0 or 2
  • r represents an integer of 0 to 3
  • s represents an integer of 0 to 4
  • t represents an integer of 1 to 4.
  • alkyl group having 1 to 8 carbon atoms represented by R c a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group, a tertiary butyl group, a tertiary butyl group, an isobutyl group, a pentyl group , Isopentyl group, neopentyl group, tertiary pentyl group, hexyl group, 1-ethylpentyl group, cyclohexyl group, 1-methylcyclohexyl group, heptyl group, isoheptyl group, tertiary heptyl group, n-octyl group, isooctyl group, Examples thereof include trioctyl group and 2-ethylhexyl group.
  • a branched alkylene group having 2 to 18 carbon atoms represented by R d is a group given by a glycol, and examples of the glycol include 1,2-ethanediol, 1, 2 -Propanediol, 1,3-propanediol, 1,3-butanediol, 2,4-hexanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol , 2,2-diethyl-1,3-butanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,4-pentanediol, 2-methyl-1,3-propanediol, 1-methyl And -2,4-pentanediol and the like.
  • examples of the alkyl group having 1 to 3 carbon atoms represented by R e and R f include a methyl group, an ethyl group, a propyl group and a 2-propyl group.
  • examples of the alkyl group having 1 to 4 carbon atoms represented by R g , R h , R j and R k include methyl, ethyl, propyl, isopropyl, butyl, butyl, sec-butyl and tert-butyl And isobutyl group.
  • precursors containing a rare earth element include compounds represented by the following formulas (III-1) to (III to 3).
  • M 2 represents a rare earth atom, and each of R a and R b may be independently substituted with a halogen atom, and may contain an oxygen atom in the chain, and an alkyl group having 1 to 20 carbon atoms.
  • R c represents an alkyl group having 1 to 8 carbon atoms
  • R e and R f each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R g and R j each represent Independently, it represents an alkyl group having 1 to 4 carbon atoms
  • p ′ represents an integer of 0 to 3
  • r ′ represents an integer of 0 to 2.
  • rare earth atoms represented by M 2 in the above-mentioned precursors containing rare earth elements scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, Ytterbium and lutetium can be mentioned.
  • Examples of the group represented by R a , R b , R c , R e , R f , R g and R j include the groups exemplified for the above-mentioned precursor containing titanium.
  • the raw material for forming a thin film of the present invention may optionally contain a nucleophile in order to impart the stability of the compound of the present invention and other precursors.
  • a nucleophile ethylene glycol ethers such as glyme, diglyme, triglyme, tetraglyme, 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8 Crown ethers such as dibenzo-24-crown-8, ethylenediamine, N, N'-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,1,4,7,7- Polyamines such as pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, triethoxytriethyleneamine, cyclic polyamines such as cyclam and cyclen, pyr
  • the raw material for thin film formation of the present invention is made to contain as much as possible impurity metal elements other than the components constituting the film, impurity halogens such as impurity chlorine, and impurity organic components.
  • the impurity metal element content is preferably 100 ppb or less, more preferably 10 ppb or less, and 1 ppm or less in total, and more preferably 100 ppb or less in each element.
  • the film is used as a gate insulating film, gate film or barrier layer of LSI, it is necessary to reduce the content of alkali metal elements and alkaline earth metal elements which affect the electric characteristics of the obtained thin film.
  • the total amount of the organic impurities is preferably 500 ppm or less, more preferably 50 ppm or less, and most preferably 10 ppm or less.
  • the precursor, the organic solvent, and the nucleophile for reducing the respective water content It is better to remove water as much as possible before use.
  • the water content of each of the precursor, the organic solvent and the nucleophile is preferably 10 ppm or less, more preferably 1 ppm or less.
  • the raw material for thin film formation of the present invention is preferably made to contain particles as little as possible.
  • the number of particles larger than 0.3 ⁇ m is preferably 100 or less in 1 mL of liquid phase, and larger than 0.2 ⁇ m
  • the number of particles is more preferably 1000 or less in 1 mL of liquid phase, and most preferably the number of particles larger than 0.2 ⁇ m is 100 or less in 1 mL of liquid phase.
  • a vapor obtained by vaporizing the raw material for thin film deposition of the present invention and a reactive gas used as needed Is introduced into a deposition chamber in which the precursor is placed, and then the precursor is decomposed and / or chemically reacted on the substrate to grow and deposit a metal-containing thin film on the substrate surface.
  • a vapor obtained by vaporizing the raw material for thin film deposition of the present invention and a reactive gas used as needed Is introduced into a deposition chamber in which the precursor is placed, and then the precursor is decomposed and / or chemically reacted on the substrate to grow and deposit a metal-containing thin film on the substrate surface.
  • Examples of the reactive gas to be used according to the above requirements include oxygen, ozone, nitrogen dioxide, nitrogen monoxide, water vapor, hydrogen peroxide, formic acid, acetic acid, acetic anhydride and the like as an oxidizing gas.
  • Examples of reducing substances include hydrogen
  • examples of producing nitrides include organic amine compounds such as monoalkylamines, dialkylamines, trialkylamines, alkylenediamines, hydrazine, ammonia and the like, Can be used alone or in combination of two or more.
  • thermal CVD to react a raw material gas or a raw material gas with a reactive gas by heat alone to deposit a thin film
  • plasma CVD using heat and plasma photo CVD using heat and light
  • thermal And photoplasma CVD using light and plasma thermal And photoplasma CVD using light and plasma
  • ALD in which the deposition reaction of CVD is divided into elementary processes and deposition is performed stepwise at the molecular level.
  • the material of the substrate is, for example, silicon; silicon oxide such as quartz; silicon nitride, titanium nitride, tantalum nitride, titanium oxide, titanium nitride, titanium nitride, ruthenium oxide, zirconium oxide, hafnium oxide, ceramics such as lanthanum oxide; Metals such as ruthenium can be mentioned.
  • silicon and silicon oxide have the property that a cobalt-containing thin film is not formed.
  • a cobalt-containing thin film can be selectively formed only on the pattern of a copper layer, a ruthenium layer or the like.
  • the shape of the substrate may be plate-like, spherical, fibrous or scaly.
  • the substrate surface may be flat or may have a three-dimensional structure such as a trench structure.
  • the above-mentioned production conditions include a reaction temperature (substrate temperature), a reaction pressure, a deposition rate and the like.
  • the reaction temperature is preferably 100 ° C. or higher at which the compound of the present invention sufficiently reacts, and more preferably 150 ° C. to 400 ° C. C. to 250.degree. C. are particularly preferred as the compounds of the present invention can be pyrolyzed below 250.degree.
  • the reaction pressure is preferably atmospheric pressure to 10 Pa in the case of thermal CVD or optical CVD, and is preferably 2000 Pa to 10 Pa in the case of using plasma.
  • the deposition rate can be controlled by the supply conditions of the raw material (evaporation temperature, evaporation pressure), reaction temperature, and reaction pressure.
  • the deposition rate is preferably 0.01 to 100 nm / min, and more preferably 1 to 50 nm / min because a high deposition rate may deteriorate the properties of the obtained thin film, and a small deposition rate may cause problems in productivity.
  • the number of cycles is controlled to obtain a desired film thickness.
  • the above-mentioned production conditions further include the temperature and pressure at the time of vaporizing the thin film forming material to form a vapor.
  • the step of vaporizing the thin film forming material into vapor may be performed in the material container or in the vaporizing chamber. In any case, it is preferable to evaporate the material for thin film formation of the present invention at 0 to 150 ° C.
  • the pressure in the material container and the pressure in the vaporization chamber are preferably each 1 to 10000 Pa.
  • the thin film production method of the present invention adopts the ALD method, and the raw material for thin film formation is vaporized into vapor by the above-mentioned transport supply method, and the raw material introduction step of introducing the vapor into the film forming chamber, A precursor thin film forming step of forming a precursor thin film on the surface of the substrate by the compound in the vapor; an exhausting step of exhausting an unreacted compound gas; and a chemical reaction of the precursor thin film with a reactive gas, You may have the metal containing thin film formation process of forming the thin film containing the said metal in the surface of this base
  • a thin film containing at least one atom selected from a copper atom, an iron atom, a nickel atom, a cobalt atom and a manganese atom by the ALD method, first, the raw material introduction step described above is performed. The preferable temperature and pressure when using the thin film forming material as a vapor are the same as those described above. Next, a precursor thin film is formed on the substrate surface by the compound introduced into the deposition reaction part (precursor thin film formation step). At this time, the substrate may be heated or the deposition reaction part may be heated to apply heat.
  • the precursor thin film formed in this step is a thin film formed from the compound of the present invention, or a thin film formed by decomposition and / or reaction of a part of the compound of the present invention, and the target metal-containing It has a different composition from the thin film.
  • Room temperature to 500 ° C. is preferable, and 150 to 350 ° C. is more preferable for the substrate temperature when this step is performed.
  • the pressure of the system (in the deposition chamber) when this step is performed is preferably 1 to 10000 Pa, and more preferably 10 to 1000 Pa.
  • unreacted compound gas and by-produced gas are exhausted from the deposition reaction unit (exhaust process).
  • Unreacted compound gas and by-produced gas are ideally exhausted completely from the deposition reaction part, but they do not necessarily have to be exhausted completely.
  • an exhaust method a method of purging the inside of the system with an inert gas such as nitrogen, helium, argon, a method of exhausting by depressurizing the inside of the system, a method combining these, and the like can be mentioned.
  • the degree of reduced pressure when reducing the pressure is preferably 0.01 to 300 Pa, and more preferably 0.01 to 100 Pa.
  • a reactive gas is introduced into the deposition reaction part, and the target metal-containing thin film is obtained from the precursor thin film obtained in the precursor thin film forming step described above by the action of the reactive gas or the action of the reactive gas and heat.
  • Metal-containing thin film forming step Room temperature to 500 ° C. is preferable, and 150 to 350 ° C. is more preferable as a temperature when heat is applied in this step.
  • the pressure of the system (in the deposition chamber) when this step is performed is preferably 1 to 10000 Pa, and more preferably 10 to 1000 Pa. Since the compound of the present invention has good reactivity with the reactive gas, a high quality metal-containing thin film with a low residual carbon content can be obtained.
  • thin film deposition by a series of operations including the above-mentioned raw material introducing step, precursor thin film forming step, exhausting step and metal containing thin film forming step
  • One cycle may be repeated several times until a thin film having a required film thickness is obtained.
  • energy such as plasma, light, voltage or the like may be applied, or a catalyst may be used.
  • the time of applying the energy and the time of using the catalyst are not particularly limited.
  • the exhaust process At the time of evacuation in the system, it may be at the time of reactive gas introduction in the metal-containing thin film formation step, or may be between the above-mentioned respective steps.
  • annealing may be performed in an inert atmosphere, in an oxidizing atmosphere, or in a reducing atmosphere to obtain better electrical characteristics. If embedding is required, a reflow process may be provided.
  • the temperature in this case is 200 to 1000 ° C., preferably 250 to 500 ° C.
  • the apparatus for manufacturing a thin film using the raw material for thin film formation of the present invention can use a known apparatus for chemical vapor deposition.
  • the apparatus include an apparatus capable of bubbling a precursor as shown in FIG. 1 and an apparatus having a vaporization chamber as shown in FIG. Further, as shown in FIG. 3 and FIG. 4, an apparatus capable of performing plasma processing on a reactive gas can be mentioned. Not limited to the single-wafer apparatus as shown in FIGS. 1 to 4, an apparatus capable of simultaneously processing multiple wafers using a batch furnace can also be used.
  • the thin film produced using the raw material for thin film formation of the present invention can be formed of a desired kind of metal, oxide ceramic, nitride ceramic, glass or the like by appropriately selecting other precursors, reactive gases and production conditions. It can be a thin film.
  • the thin film is known to exhibit various electrical and optical properties and the like, and is applied to various applications.
  • copper and copper-containing thin films are applied as wiring materials for LSIs because of their properties of high conductivity, high electromigration resistance, and high melting point.
  • Nickel and nickel-containing thin films are mainly used as members of electronic parts such as resistive films and barrier films, members for recording media such as magnetic films, and members for thin film solar cells such as electrodes.
  • Cobalt and cobalt-containing thin films are used for electrode films, resistance films, adhesive films, magnetic tapes, cemented carbide tools and the like.
  • the amidine compound of the present invention is a compound represented by the following general formula (2), and is a compound particularly suitable as a ligand of a precursor used in a thin film production method having a vaporization process such as a CVD method.
  • R 5 represents a linear or branched alkyl group having 1 to 5 carbon atoms
  • R 6 represents hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms
  • R 7 And R 8 each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms
  • L represents an alkanediyl group having 1 to 4 carbon atoms, provided that R 5 is an ethyl group and
  • R 6 is hydrogen, L is a branched alkanediyl group having 3 carbon atoms, or an alkanediyl group having 4 carbon atoms, and R 5 is an ethyl group or a tertiary butyl group and R 6
  • L is a methyl group
  • L is an alkanediyl group having 3 or 4 carbon atoms.
  • Examples of the linear or branched alkyl group having 1 to 5 carbon atoms represented by R 5 , R 6 , R 7 and R 8 in the above general formula (2) include, for example, a methyl group, an ethyl group, and a propyl group.
  • Examples of the alkanediyl group having 1 to 4 carbon atoms represented by L in the general formula (2) include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group. Groups, butylene group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2-diyl group and the like.
  • R 5 is preferably an isopropyl group, an isobutyl group, a secondary butyl group or a tertiary butyl group.
  • an amidine compound in which R 5 is a tertiary butyl group is preferable because of its good stability.
  • an amidine compound in which R 6 is hydrogen, a methyl group or an ethyl group is preferably a metal complex compound having a high vapor pressure when it is used as a ligand of the metal complex compound.
  • an amidine compound in which L is an ethylene group, propane-1,3-diyl group or propane-1,2-diyl group has a melting point when it is a ligand of a metal complex compound. It is preferable because a metal complex compound having a low vapor pressure and a high vapor pressure is obtained. Among them, amidine compounds in which L is a propane-1,2-diyl group are particularly preferable.
  • an amidine compound in which R 7 and R 8 are a methyl group or an ethyl group gives a metal complex compound having a low melting point and a high vapor pressure when used as a ligand of a metal complex compound. It is preferable from being Among them, amidine compounds in which R 7 and R 8 are methyl groups are particularly preferable.
  • amidine compound represented by the above general formula (2) include, for example, the following compound No. 1; 55-156.
  • compound No. 1 represents a methyl group
  • Et represents an ethyl group
  • iPr represents an isopropyl group
  • sBu represents a sec-butyl group
  • tBu is a tert-butyl group Represents a group.
  • the amidine compound of the present invention is not particularly limited by the production method thereof, and can be produced by applying a known reaction.
  • a carbodiimide compound is synthesized as an intermediate by reacting with trialkylamine and p-toluenesulfonic acid chloride using dichloromethane or the like as a solvent.
  • the product can be produced by purifying an alkyllithium dialkyl ether reacted thereto by a method such as distillation.
  • the amidine compound of the present invention can be used as a ligand of a metal complex compound used as a thin film forming material or the like.
  • the amidine compound of the present invention can also be used for applications such as solvents, perfumes, pesticides, medicines, synthetic raw materials such as various polymers, and the like.
  • Example 1 Compound No. 1 Preparation of 151 In a 2 L four-necked flask, 21.3 g (0.215 mol) of tertbutyl isocyanate and 131.7 g of diethyl ether were charged, and stirred under water cooling. To this solution was added dropwise a solution of 22.1 g (0.216 mol) of N, N-dimethylpropane-1,2-diamine and 55.6 g of diethyl ether. After dropping, the mixture was returned to room temperature and stirred for 3 hours. Thereafter, the solvent was removed under slight pressure at an oil bath of 60 ° C.
  • Example 2 Compound No. Preparation of 2 In a 500 mL four-necked flask, 8.60 g (0.066 mol) of cobalt (II) chloride and 69.5 g of tetrahydrofuran were charged and stirred at room temperature. Among them, the compound No. 151 A solution prepared by 24.4 g (0.132 mol), 85.6 g of normal hexane, and 57.6 g (0.132 mol) of nBuLi is added dropwise with ice cooling, and after the addition, the solution is returned to room temperature and stirred for 17 hours, followed by filtration.
  • the solvent was removed from the obtained filtrate, and the residue was distilled at a bath temperature of 160 ° C., a pressure of 77 Pa and an overhead temperature of 132 ° C. to obtain the desired product as a dark green liquid.
  • the yield was 20.0 g, 66%.
  • Example 3 Compound No. 3 Preparation of 1 In a 300 mL three-necked flask, 5.31 g (0.041 mol) of cobalt (II) chloride and 74.9 g of tetrahydrofuran were charged and stirred at room temperature. A solution prepared from 15.30 g (0.083 mol) of a known compound A, 65.9 g of normal hexane and 35.2 g (0.082 mol) of nBuLi is added dropwise thereto under ice cooling, and the solution is returned to room temperature and stirred for 19 hours And filtered. The solvent was removed from the obtained filtrate, and the residue was purified by Kugelrohr at a temperature of 130 ° C. and a pressure of 57 Pa to obtain a dark green solid.
  • Example 4 Compound No. 4 Preparation of 157 18.8 g (0.190 mol) of tert butyl isocyanate and 129.7 g of diethyl ether were charged in a 2 L four-necked flask and stirred under water cooling. To this solution was added dropwise a solution of 19.4 g (0.190 mol) of N, N-dimethyl-1,3-propanediamine and 45.4 g of diethyl ether. After dropping, the mixture was returned to room temperature and stirred for 3 hours. Thereafter, solvent removal was carried out under a slightly reduced pressure of an oil bath at 70 ° C.
  • Example 5 Compound No. 5 Preparation of 158
  • 1.72 g (0.013 mol) of cobalt (II) chloride and 23.9 g of tetrahydrofuran were charged and stirred at room temperature.
  • the compound No. A solution prepared from 5.20 g (0.026 mol) of 157, 20.9 g of normal hexane, and 11.4 g (0.026 mol) of nBuLi is added dropwise under ice cooling, and after returning to room temperature it is returned to room temperature and stirred for 16 hours and filtered.
  • the solvent was removed from the obtained filtrate, and the residue was purified by Kugelrohr at a temperature of 145 ° C. and a pressure of 59 Pa to obtain a dark green liquid (Compound No. 158 shown below).
  • the yield was 0.51 g, 8%.
  • Example 6 Compound No. 6 Preparation of 159 In a 500 mL four-necked flask, 10.0 g (0.055 mol) of a carbodiimide compound A and 78.6 g of diethyl ether were charged, and stirred under ice-cooling. To this solution was added dropwise 230 ml (0.115 mol) of an ethyllithium benzenecyclohexane solution. After dropping, the mixture was returned to room temperature and stirred for 48 hours, and then heated to reflux for 23 hours. After cooling to room temperature, water was added dropwise under ice-cooling to complete the reaction, the organic layer was extracted and partitioned, sodium sulfate was added, and dehydration and filtration were performed.
  • Example 7 Compound No. 7 Preparation of 8 In a 200 mL four-necked flask, 2.66 g (0.020 mol) of cobalt (II) chloride and 25.0 g of tetrahydrofuran were charged and stirred at room temperature. Among them, the compound No. A solution prepared from 9.20 g (0.040 mol) of 159, 23.3 g of normal hexane and 20.2 g (0.047 mol) of nBuLi is added dropwise with ice cooling, and after returning to the room temperature, it is returned to room temperature and stirred for 16 hours and filtered.
  • the solvent was removed from the obtained filtrate, and the residue was distilled at a bath temperature of 170 ° C., a pressure of 26 Pa, and an overhead temperature of 122 ° C. to obtain a dark green liquid.
  • the yield was 4.0 g, 40%.
  • Example 8 Compound No. Preparation of 127
  • 24.1 g (0.237 mol) of isopropyl isothiocyanate and 385.8 g of diethyl ether were charged and stirred under water cooling.
  • To this solution was added dropwise a solution of 26.9 g (0.263 mol) of N, N-dimethylpropane-1,2-diamine and 119.8 g of diethyl ether. After dropping, the mixture was returned to room temperature and stirred for 14 hours. Thereafter, solvent removal was carried out under a slightly reduced pressure of an oil bath at 65 ° C.
  • Example 9 Preparation of 160 In a 200 mL four-necked flask, 2.34 g (0.018 mol) of cobalt (II) chloride and 22.7 g of tetrahydrofuran were charged and stirred at room temperature. Among them, the compound No. 127 A solution prepared by 6.50 g (0.035 mol), 21.6 g of normal hexane and 15.6 g (0.035 mol) of nBuLi was added dropwise under ice-cooling, and the solution was returned to room temperature and stirred for 16 hours, followed by filtration. .
  • Example 10 Compound No. Preparation of 139 25.1 g (0.218 mol) of sec-butyl isothiocyanate and 165.9 g of diethyl ether were charged in a 2 L four-necked flask and stirred under water cooling. To this solution was added dropwise a solution of 24.3 g (0.238 mol) of N, N-dimethylpropane-1,2-diamine and 83.6 g of diethyl ether. After dropping, the temperature was returned to room temperature and stirred for 19 hours. Thereafter, solvent removal was carried out under slightly reduced pressure of an oil bath at 75 ° C.
  • Example 11 Compound No. Preparation of 161 In a 200 mL four-necked flask, 1.71 g (0.013 mol) of cobalt (II) chloride and 15.1 g of tetrahydrofuran were charged, and stirred at room temperature. Among them, the compound No. A solution prepared from 5.25 g (0.026 mol) of 139, 17.1 g of normal hexane and 11.2 g (0.026 mol) of nBuLi was added dropwise under ice-cooling, and after the addition, the solution was returned to room temperature and stirred for 21 hours, followed by filtration. .
  • the solvent was removed from the obtained filtrate, and the residue was distilled at a bath temperature of 165 ° C., a pressure of 40 Pa, and an overhead temperature of 127 ° C. to obtain a dark green liquid (Compound No. 161 shown below).
  • the yield was 3.5 g, 59%.
  • Comparative Compound 1 was a compound having a melting point of 105 ° C. It turned out that 2, 8, 158, 160 and 161 are compounds which are liquid under conditions of normal pressure 30 ° C. The material for thin film formation having a low melting point is a material for thin film formation which can improve productivity because it is easy to transport. Further, from the results of reduced pressure TG-DTA, it was found that compound No. It was found that although 1, 2, 8, 158, 160 and 161 had a temperature slightly reduced by 50% by mass compared with Comparative Compound 1, they exhibited a sufficient vapor pressure as a raw material for chemical vapor deposition.
  • Example 12 Production of metallic cobalt thin film by ALD method
  • the metal cobalt thin film was manufactured on a ruthenium (Ru) substrate by ALD method of the following conditions using the apparatus for chemical vapor deposition shown in FIG. 1 by using 2 as a raw material for chemical vapor deposition.
  • the obtained thin film was subjected to film thickness measurement by X-ray reflectance method, X-ray diffraction method and X-ray photoelectron spectroscopy to confirm the thin film structure and thin film composition, and the film thickness was 1 to 3 nm. Is metallic cobalt (confirmed by Co2p peak by XPS analysis), and the residual carbon content in the thin film was less than the detection limit of 0.1 atom%.
  • the film thickness obtained per cycle was 0.01 to 0.03 nm.
  • Example 13 Production of Metallic Cobalt Thin Film by ALD Method
  • a metallic cobalt thin film was produced in the same manner as in Example 12 except that 1 was used as a raw material for chemical vapor deposition.
  • the film thickness was 0.5 to 1.5 nm
  • the film composition was metallic cobalt (confirmed by Co2p peak by XPS analysis), and the residual carbon content in the thin film was 0.5 atom%.
  • the film thickness obtained per cycle was 0.005 to 0.015 nm.
  • Example 12 Compound No.
  • Metallic cobalt thin films were produced in the same manner as in Example 12, except that each of 8, 158, 160 and 161 was used as a chemical vapor deposition material.
  • the obtained thin film was subjected to film thickness measurement by X-ray reflectance method, X-ray diffraction method and X-ray photoelectron spectroscopy to confirm the thin film structure and thin film composition, and the film thickness was 1 to 2 nm.
  • Is metallic cobalt confirmeded by Co2p peak by XPS analysis
  • the film thickness obtained per cycle was 0.01 to 0.02 nm.
  • Comparative Example 1 Using the comparative compound 1 as a raw material for chemical vapor deposition and using the apparatus for chemical vapor deposition shown in FIG. 1, a metallic cobalt thin film was produced on a Ru substrate by the ALD method under the following conditions.
  • the thin film obtained on Ru substrate when the thin film structure and thin film composition were confirmed by film thickness measurement by X-ray reflectance method, X-ray diffraction method and X-ray photoelectron spectroscopy, the film thickness was 1 to 2 nm
  • the film composition was metallic cobalt (confirmed by Co2p peak by XPS analysis), and the residual carbon content in the thin film was 5 atom% or more.
  • the film thickness obtained per cycle was 0.01 to 0.02 nm.
  • Reaction temperature (substrate temperature); 200 ° C, reactive gas; hydrogen gas (process)
  • the source material for chemical vapor deposition vaporized under the conditions of 100 Pa is introduced into a film forming chamber and deposited for 30 seconds at a system pressure of 100 Pa.
  • Reactive gas is introduced into the film forming chamber and reacted for 30 seconds at a system pressure of 100 Pa.
  • Example 14 Production of Metallic Cobalt Thin Film by ALD Method
  • a thin film was formed only on the Ru layer.
  • the film thickness was 1 to 3 nm
  • the film composition was metallic cobalt (confirmed by Co2p peak by XPS analysis), and the residual carbon content in the thin film was less than the detection lower limit of 0.1 atom%.
  • the film thickness obtained per cycle was 0.01 to 0.03 nm.
  • metallic cobalt was not detected from the exposed portion of SiO 2 of the substrate.
  • Example 15 Production of Metallic Cobalt Thin Film by ALD Method
  • a metallic cobalt thin film was produced in the same manner as in Example 14 except that 1 was used as a raw material for chemical vapor deposition. As a result, a thin film was formed only on the part of the Ru layer.
  • the thin film structure and thin film composition were confirmed by the film thickness measurement by the X-ray reflectance method, the X-ray diffraction method and the X-ray photoelectron spectroscopy, The film composition was metallic cobalt (confirmed by Co2p peak by XPS analysis), and the residual carbon content in the thin film was 0.5 atom%.
  • the film thickness obtained per cycle was 0.005 to 0.015 nm.
  • Example 14 Compound No.
  • Metallic cobalt thin films were produced in the same manner as in Example 14 except that each of 8, 158, 160 and 161 was used as a chemical vapor deposition material. As a result, a thin film was formed only on the part of the Ru layer.
  • the thin film obtained on the Ru layer was subjected to film thickness measurement by X-ray reflectance method, X-ray diffraction method and X-ray photoelectron spectroscopy to confirm the thin film structure and the thin film composition.
  • the film composition was metallic cobalt (confirmed by Co2p peak by XPS analysis), and the residual carbon content in the thin film was 0.2 atom%.
  • the film thickness obtained per cycle was 0.01 to 0.02 nm.

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US11161867B2 (en) 2021-11-02
KR102503603B1 (ko) 2023-02-23
EP3539973A1 (en) 2019-09-18
JP7075891B2 (ja) 2022-05-26
US20220017554A1 (en) 2022-01-20
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TW201829823A (zh) 2018-08-16
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